Optimization of the electrodeposition of copper on poly-1-naphthylamine for the amperometric detection of carbohydrates in HPLC.

A modified electrode consisting of copper dispersed in a poly-1-naphthylamine (p-1-NAP/Cu) film on a glassy carbon electrode was used as an amperometric detector for the on-line analysis of various carbohydrates separated by high performance liquid chromatography. The results obtained with this new sensor were compared to those obtained with a modified electrode based on the same polymer but with copper ions incorporated at open circuit, as described in a previous paper. In this new modified electrode the copper microparticles were electrochemically deposited into the polymeric matrix by single potential step chronoamperometry. A nucleation and growth mechanism was proposed to explain the current transients of copper electrodeposition. The experimental results were fitted to the proposed mechanism by using a mathematical equation that considers three-dimensional growth and progressive nucleation, assuming a no overlap and no diffusion mechanism. Cyclic voltammetric experiments showed that the electrodeposited copper microparticles provided a catalytic surface suited for the oxidation of glucose and several carbohydrates. The sensitivity of the electrode was influenced by the amount of copper electrodeposited, which in turn depended on the applied overpotential used for the deposition of copper. Liquid chromatographic experiments were carried out to test the analytical performance of these electrodes for the determination of various carbohydrates.